WO2019188520A1 - Peau, procédé de production de peau et produit en couches - Google Patents

Peau, procédé de production de peau et produit en couches Download PDF

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Publication number
WO2019188520A1
WO2019188520A1 PCT/JP2019/011264 JP2019011264W WO2019188520A1 WO 2019188520 A1 WO2019188520 A1 WO 2019188520A1 JP 2019011264 W JP2019011264 W JP 2019011264W WO 2019188520 A1 WO2019188520 A1 WO 2019188520A1
Authority
WO
WIPO (PCT)
Prior art keywords
vinyl chloride
chloride resin
molded sheet
resin molded
skin
Prior art date
Application number
PCT/JP2019/011264
Other languages
English (en)
Japanese (ja)
Inventor
翔太 西村
Original Assignee
日本ゼオン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to US16/980,846 priority Critical patent/US20210017373A1/en
Priority to CN201980017537.XA priority patent/CN111886377A/zh
Priority to MX2020009641A priority patent/MX2020009641A/es
Priority to EP19774975.7A priority patent/EP3779033B1/fr
Priority to JP2020510708A priority patent/JP7310799B2/ja
Publication of WO2019188520A1 publication Critical patent/WO2019188520A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/23—Azo-compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0221—Vinyl resin
    • B32B2266/0235—Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0242—Acrylic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/022—Foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2327/00—Polyvinylhalogenides
    • B32B2327/06—PVC, i.e. polyvinylchloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2427/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present invention relates to a skin, a method for producing a skin, and a laminate.
  • Vinyl chloride resins are generally used in various applications because they are excellent in properties such as cold resistance, heat resistance, and oil resistance.
  • a vinyl chloride resin molded body obtained by molding a vinyl chloride resin composition into a sheet (hereinafter referred to as “vinyl chloride resin molded sheet”).
  • Automobile interior materials such as a laminate formed by lining a foam made of foamed polyurethane or the like on a skin made of a vinyl chloride resin molded sheet or a skin made of the vinyl chloride resin molded sheet.
  • a vinyl chloride resin composition containing a vinyl chloride resin and a plasticizer is used (for example, see Patent Documents 1 and 2).
  • the skin made of a vinyl chloride resin molded sheet containing a plasticizer shrinks under high-temperature conditions when used with a foamed body such as a polyurethane foam molded body, so that the design as an automobile interior material is impaired. There was a problem of being. Therefore, it is required to suppress thermal shrinkage of the skin when the foamed polyurethane molded body is used as a backing.
  • an object of the present invention is to provide a skin capable of satisfactorily suppressing thermal shrinkage when a foamed polyurethane molded body is used as a backing. Furthermore, an object of this invention is to provide the laminated body provided with the said skin and which can suppress heat shrink favorably.
  • the present inventor has intensively studied for the purpose of solving the above problems.
  • the inventor used a foamed polyurethane molded article as a backing if it is a skin formed by placing a foamed vinyl chloride resin molded sheet on one side in the thickness direction of a vinyl chloride resin molded sheet containing a plasticizer. In some cases, it was found that heat shrinkage of the epidermis can be satisfactorily suppressed, and the present invention was completed.
  • the skin of the present invention comprises a vinyl chloride resin molded sheet (X) containing a vinyl chloride resin and a plasticizer, and foamed vinyl chloride.
  • Resin molded sheet (Y), and the plasticizer content in the vinyl chloride resin molded sheet (X) is 50 parts by mass or more per 100 parts by mass of the vinyl chloride resin, and the foam
  • the vinyl chloride resin molded sheet (Y) is arranged on one side in the thickness direction of the vinyl chloride resin molded sheet (X).
  • the thickness of the said foaming vinyl chloride resin molded sheet (Y) is 1.5 mm or more.
  • the thickness of the foamed vinyl chloride resin molded sheet (Y) can be measured using an optical microscope.
  • the foamed vinyl chloride resin molded sheet (Y) contains an acrylic polymer. If the foamed vinyl chloride resin molded sheet (Y) contains an acrylic polymer, the hardness of the skin can be reduced.
  • the acrylic polymer contains a copolymer of methacrylic acid alkyl ester and acrylic acid alkyl ester. If the acrylic polymer includes a copolymer of methacrylic acid alkyl ester and acrylic acid alkyl ester, the hardness of the skin can be further reduced.
  • the skin of the present invention is preferably used for the skin of automobile interior parts. If the skin of the present invention is used as the skin of an automobile interior part, it is possible to satisfactorily suppress thermal shrinkage when the foamed polyurethane molded article is used as a backing, and to prevent deterioration of the skin.
  • the manufacturing method of the skin of this invention is a manufacturing method of the skin which has a vinyl chloride resin molded sheet (X) and a foamed vinyl chloride resin molded sheet (Y), and contains a vinyl chloride resin and a plasticizer.
  • a second step of forming a foamed vinyl chloride resin molded sheet (Y) using B) wherein the content of the plasticizer in the vinyl chloride resin composition (A) is 100% of the vinyl chloride resin 100. It is 50 mass parts or more per mass part.
  • a step of forming a vinyl chloride resin molded sheet using a vinyl chloride resin composition containing a vinyl chloride resin and a plasticizer, and one side in the thickness direction of the vinyl chloride resin molded sheet By carrying out the step of forming a foamed vinyl chloride resin molded sheet using the resin composition, it is possible to produce a skin that can satisfactorily suppress thermal shrinkage when the foamed polyurethane molded body is used as a backing. .
  • the foamable vinyl chloride resin composition (B) preferably contains a pyrolytic foaming agent. If the foamable vinyl chloride resin composition (B) contains a pyrolytic foaming agent, thermal shrinkage can be further suppressed when the foamed polyurethane molded body is lined on the resulting skin.
  • the pyrolyzable foaming agent contains an azo compound.
  • the pyrolytic foaming agent contains an azo compound, thermal shrinkage can be further suppressed when the foamed polyurethane molded body is used as a backing on the obtained skin.
  • the volume average particle diameter of the pyrolytic foaming agent is 10 ⁇ m or less. If the volume average particle diameter of the pyrolytic foaming agent is 10 ⁇ m or less, the hardness of the resulting skin can be lowered and cushioning properties can be improved.
  • the laminated body of this invention is a laminated body which has a foaming polyurethane molded object and one of the skins mentioned above,
  • the foamed vinyl chloride resin molded sheet (Y) is disposed between the foamed polyurethane molded body and the vinyl chloride resin molded sheet (X).
  • the foamed vinyl chloride resin molded sheet (Y) is disposed between the foamed polyurethane molded body and the vinyl chloride resin molded sheet (X).
  • it has a polyurethane foam molded article and any one of the above-mentioned skins, and the foamed vinyl chloride resin molded sheet (Y) between the polyurethane foam molded article and the vinyl chloride resin molded sheet (X). If it is a laminated body by which heat
  • the present invention it is possible to provide a skin that can satisfactorily suppress thermal shrinkage when a foamed polyurethane molded article is used as a backing. Moreover, according to this invention, the laminated body which can suppress the heat contraction of an epidermis favorably can be provided.
  • the skin of this invention can be used for manufacture of the laminated body of this invention, for example.
  • the skin of the present invention can be suitably used as an automobile interior material such as the skin of automobile interior parts such as an automobile instrument panel.
  • the skin of this invention can be manufactured with the manufacturing method of the skin of this invention.
  • the skin of the present invention has a vinyl chloride resin molded sheet (X) containing a vinyl chloride resin and a predetermined amount of plasticizer, and a foamed vinyl chloride resin molded sheet (Y). ) Is disposed on one side in the thickness direction of the vinyl chloride resin molded sheet (X). And, since the foamed vinyl chloride resin molded sheet (Y) is disposed on one side in the thickness direction of the vinyl chloride resin molded sheet (X), the skin of the present invention is used by lining the polyurethane foam molded body.
  • the skin of the present invention is suitably used as an automotive interior member, specifically, for example, as a skin of automotive interior parts such as automotive instrument panels and door trims, and particularly for the skin of automotive instrument panels. Is preferably used.
  • the vinyl chloride resin molded sheet (X) is obtained by molding a vinyl chloride resin composition (A) containing a vinyl chloride resin and a predetermined amount of a plasticizer into a sheet shape.
  • the vinyl chloride resin molded sheet (X) is usually not a foam unlike the foamed vinyl chloride resin molded sheet (Y) described later.
  • the thickness of the vinyl chloride resin molded sheet (X) is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.5 mm or more, and further preferably 0.7 mm or more. 1.0 mm or more, more preferably 1.2 mm or more, preferably 5.0 mm or less, more preferably 2.0 mm or less, and 1.8 mm or less. More preferably, it is 1.5 mm or less. This is because, if the thickness of the vinyl chloride resin molded sheet (X) is not less than the above lower limit, the resulting vinyl chloride resin molded sheet (X) can be imparted with good tensile elongation at low temperatures.
  • the resulting vinyl chloride resin molded sheet (X) is excellent in handleability, and the foamed vinyl chloride resin is added to the vinyl chloride resin molded sheet (X). This is because the molded sheet (Y) can be arranged more easily.
  • the vinyl chloride resin composition (A) contains a vinyl chloride resin and a predetermined amount of a plasticizer, and may optionally further contain various additives. Except for components that can be decomposed in the molding step, the content of each component in the vinyl chloride resin composition (A) relative to the vinyl chloride resin is relative to the vinyl chloride resin of each component in the vinyl chloride resin molded sheet (X). It shall be consistent with the content.
  • the vinyl chloride resin contained in the vinyl chloride resin composition (A) can contain, for example, one type or two or more types of vinyl chloride resin particles, and optionally one type or two or more types of chloride. Vinyl resin fine particles can be further contained.
  • the vinyl chloride resin preferably contains at least vinyl chloride resin particles, and more preferably contains vinyl chloride resin particles and vinyl chloride resin fine particles.
  • “resin particles” refers to particles having a particle size of 30 ⁇ m or more, and “resin particles” refers to particles having a particle size of less than 30 ⁇ m.
  • the vinyl chloride resin particles usually function as a matrix resin (base material), and the vinyl chloride resin fine particles normally function as a dusting agent (powder fluidity improver).
  • the vinyl chloride resin particles are preferably produced by a suspension polymerization method, and the vinyl chloride resin fine particles are preferably produced by an emulsion polymerization method.
  • the vinyl chloride resin can be produced by any conventionally known production method such as suspension polymerization method, emulsion polymerization method, solution polymerization method, bulk polymerization method and the like.
  • vinyl chloride resin in addition to a homopolymer composed of vinyl chloride monomer units, vinyl chloride copolymers containing vinyl chloride monomer units are preferably 50% by mass or more, more preferably 70% by mass or more. Can be mentioned.
  • a monomer (comonomer) copolymerizable with a vinyl chloride monomer that can constitute a vinyl chloride copolymer include olefins such as ethylene and propylene; allyl chloride, vinylidene chloride, Halogenated olefins such as vinyl fluoride and ethylene trifluoride chloride; vinyl acetates such as vinyl acetate and vinyl propionate; vinyl ethers such as isobutyl vinyl ether and cetyl vinyl ether; allyl-3-chloro-2-oxypropyl Allyl ethers such as ether and allyl glycidyl ether; unsaturated carboxylic acids such as acrylic acid, maleic acid, itaconic acid, 2-hydroxyethyl acrylate, methyl methacrylate, monomethyl maleate, diethyl maleate, maleic anhydride, Its esters or acid anhydrides; Unsaturated nitriles such as acrylonitrile and meth, vinyl
  • the monomers exemplified above are only a part of the comonomer, and examples of the comonomer include “polyvinyl chloride” edited by the Kinki Chemical Association Vinyl Division, Nikkan Kogyo Shimbun (1988), No. 75- Various monomers exemplified on page 104 can be used. These comonomer may use only 1 type and may use 2 or more types.
  • the vinyl chloride resin includes ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene, and other resins such as (1) vinyl chloride or ( 2) A resin obtained by graft polymerization of vinyl chloride and the comonomer is also included.
  • (meth) acryl means acrylic and / or methacrylic.
  • the vinyl chloride resin composition (A) further contains a predetermined amount of plasticizer. If the vinyl chloride resin composition does not contain a plasticizer, a vinyl chloride resin molded sheet cannot be satisfactorily obtained using the vinyl chloride resin composition.
  • the content of the plasticizer needs to be 50 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin, preferably 55 parts by mass or more, and preferably 60 parts by mass or more. More preferably, it is more preferably 65 parts by mass or more, still more preferably 70 parts by mass or more, still more preferably 85 parts by mass or more, and preferably 200 parts by mass or less, and 170 parts by mass. More preferably, it is 140 mass parts or less, More preferably, it is 100 mass parts or less. If the content of the plasticizer is not less than the above lower limit, the vinyl chloride resin composition (A) is provided with excellent flexibility, and can be easily processed into, for example, a vinyl chloride resin molded sheet (X) and obtained.
  • a primary plasticizer and a secondary plasticizer described in International Publication No. 2016/098344 can be used. These components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • a primary plasticizer as the plasticizer from the viewpoint of easily obtaining the vinyl chloride resin composition (A) and the vinyl chloride resin molded sheet (X). More preferably, an agent and a secondary plasticizer are used in combination.
  • the plasticizer it is preferable to use trimellitic acid ester and / or pyromellitic acid ester, more preferably at least trimellitic acid ester, and trimellitic acid ester and epoxidized soybean oil are used. It is more preferable to use together.
  • the vinyl chloride resin composition (A) may further contain various additives in addition to the components described above.
  • the additive is not particularly limited and includes, for example, stabilizers such as perchloric acid-treated hydrotalcite, zeolite, ⁇ -diketone, and fatty acid metal salt; mold release agent; Sting agents; impact resistance improvers; perchloric acid compounds other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.); antioxidants; fungicides; flame retardants; Examples thereof include fillers; light stabilizers; moldability control agents (silicone oil and the like); and colorants.
  • Such additives are not particularly limited, and for example, those described in International Publication No. 2016/098344 (excluding the foaming agent) can be used.
  • the vinyl chloride resin composition (A) is not particularly limited and can be prepared by mixing the components described above.
  • a mixing method of the vinyl chloride resin, a predetermined amount of plasticizer, and various additives further used as necessary is not particularly limited.
  • the method of mixing the component except a sting agent by dry blending, and then adding and mixing a dusting agent is mentioned.
  • the temperature at the time of dry blending is not specifically limited, 50 degreeC or more is preferable, 70 degreeC or more is more preferable, and 200 degreeC or less is preferable.
  • the skin of the present invention has a foamed vinyl chloride resin molded sheet (Y) disposed on one side in the thickness direction of the above-described vinyl chloride resin molded sheet (X). And it is preferable that a foaming vinyl chloride resin molded sheet (Y) is located in the surface of the one side of the thickness direction of the skin of this invention.
  • the surface on one side in the thickness direction of the skin of the present invention may be partially composed of a foamed vinyl chloride resin molded sheet (Y) or entirely composed of a foamed vinyl chloride resin molded sheet (Y). May be.
  • the plasticizer in the skin becomes the foamed urethane molded body. It is believed that the migration reduces the amount of plasticizer in the epidermis and causes heat shrinkage of the epidermis.
  • the vinyl chloride resin molded sheet (Y) is disposed on one side in the thickness direction of the vinyl chloride resin molded sheet (X) containing the plasticizer
  • the vinyl chloride resin molded sheet ( The plasticizer moves from the vinyl chloride resin molded sheet (X) and the foamed vinyl chloride resin molded sheet (Y) by interposing the foamed vinyl chloride resin molded sheet (Y) between the X) and the urethane foam molded body.
  • the foamed vinyl chloride resin molded sheet (Y) may be directly bonded to the vinyl chloride resin molded sheet (X), and as long as the desired effect is obtained, the foamed vinyl chloride resin molded sheet (Y) May be adhered to the vinyl chloride resin molded sheet (X) through the like, but from the viewpoint of further suppressing the thermal shrinkage when the foamed urethane molded body is used as the outer skin, the foamed vinyl chloride resin is used.
  • the molded sheet (Y) is preferably directly bonded to the vinyl chloride resin molded sheet (X).
  • the thickness of the foamed vinyl chloride resin molded sheet (Y) is not particularly limited, but is preferably 1.5 mm or more, more preferably 1.8 mm or more, and further preferably 2.0 mm or more. Preferably, it is 2.3 mm or more, more preferably 2.5 mm or more, more preferably 10.0 mm or less, more preferably 5.0 mm or less, and 4.0 mm or less. Is more preferably 3.0 mm or less, and even more preferably 2.7 mm or less.
  • the thickness of the foamed vinyl chloride resin molded sheet (Y) is equal to or greater than the above lower limit, when the foamed polyurethane molded body is lined and used on the resulting skin, the heat shrinkage of the skin can be further satisfactorily suppressed. The hardness of the epidermis can be reduced and the cushioning property can be improved. On the other hand, if the thickness of the foamed vinyl chloride resin molded sheet (Y) is less than or equal to the above upper limit, the resulting skin is excellent in handleability when backing the foamed polyurethane molded body.
  • the foamed vinyl chloride resin molded sheet (Y) is not particularly limited, but is usually obtained by molding the foamable vinyl chloride resin composition (B) into a sheet shape while foaming.
  • the foamable vinyl chloride resin composition (B) contains a vinyl chloride resin and a foaming agent, and may optionally further contain an acrylic polymer, a plasticizer, and other various additives.
  • the vinyl chloride resin contained in the foamable vinyl chloride resin composition (B) the vinyl chloride resin contained in the vinyl chloride resin composition (A) described above in the section of “vinyl chloride resin molded sheet (X)” is used. Can be used.
  • the foamable vinyl chloride resin composition (B) can contain, the plasticizer in the vinyl chloride resin composition (A) described above in the section of “vinyl chloride resin molded sheet (X)” is used. It can select suitably within the range of a kind.
  • the content of the plasticizer in the foamable vinyl chloride resin composition (B) is preferably 70 parts by mass or more, more preferably 75 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin. 80 parts by mass or more, more preferably 85 parts by mass or more, preferably 200 parts by mass or less, more preferably 170 parts by mass or less, and 140 parts by mass or less. More preferably.
  • the hardness of the said skin can be reduced and cushioning properties can be improved.
  • the content of the plasticizer in the foamable vinyl chloride resin composition (B) is not more than the above upper limit, the foamed vinyl chloride resin molded sheet (Y) is not too soft, and the resulting skin is a polyurethane foam molded product. It will be excellent in handleability when backing up.
  • the foamable vinyl chloride resin composition (B) can contain, the vinyl chloride resin composition (described above in the section of “vinyl chloride resin molded sheet (X)”) ( Additives that A) may contain can be used.
  • the content of each component in the foamable vinyl chloride resin composition (B) with respect to the vinyl chloride resin excluding components that can be decomposed in the molding step such as a pyrolytic foaming agent described later, is a foamed vinyl chloride resin molded article. It shall correspond with content with respect to the vinyl chloride resin of each component in (Y).
  • the foamable vinyl chloride resin composition (B) contains a foaming agent.
  • the foamable vinyl chloride resin composition (B) contains a foaming agent
  • the foamable vinyl chloride resin composition (B) is molded while being foamed to obtain a foamed vinyl chloride resin molded sheet (Y). Can do.
  • a foaming agent contained in the foamable vinyl chloride resin composition (B) a chemical foaming agent and a physical foaming agent can be used.
  • examples of the chemical foaming agent include a pyrolytic foaming agent and a reactive foaming agent.
  • pyrolytic foaming agent examples include organic pyrolytic foaming agents such as azo compounds, nitroso compounds, hydrazine derivatives, semicarbazide compounds, tetrazole compounds, and organic acids; bicarbonates, carbonates, organic acid salts, An inorganic pyrolytic foaming agent such as nitrate can be used.
  • examples of the azo compound include azodicarbonamide (ADCA), azobisisobutyronitrile (AIBN), barium azodicarboxylate, diazoaminobenzene, and the like.
  • examples of the nitroso compound include dinitrosopentamethylenetetramine (DPT).
  • examples of the hydrazine derivative include p, p′-oxybis (benzenesulfonylhydrazide) (OBSH), paratoluenesulfonyl hydrazide (TSH), hydrazodicarbonamide (HDCA), and the like.
  • examples of the semicarbazide compound include p-toluenesulfonyl semicarbazide.
  • Examples of the tetrazole compound include 5-phenyltetrazole and 1,4-bistetrazole.
  • Examples of the organic acid include polyvalent carboxylic acids such as citric acid, oxalic acid, fumaric acid, phthalic acid, malic acid, and tartaric acid.
  • examples of the reactive foaming agent include a combination of an isocyanate compound and water, a combination of sodium bicarbonate and acid, a combination of hydrogen peroxide and yeast, a combination of zinc powder and acid, and the like.
  • examples of physical foaming agents include gases such as chlorofluorocarbon and carbon dioxide; volatile liquids such as water and volatile hydrocarbon compounds; and thermally expandable microcapsules enclosing these gases and volatile liquids. Can be mentioned.
  • thermal decomposition type foaming agent more preferably an azo compound, and particularly preferably azodicarbonamide (ADCA).
  • a thermal decomposition type foaming agent is used as the foaming agent, thermal shrinkage can be further suppressed when a foamed polyurethane molded article is lined on the resulting skin, and an azo compound can be used as the thermal decomposition type foaming agent.
  • the thermal shrinkage when the foamed polyurethane molded body is lined on the obtained skin can be suppressed more favorably.
  • the volume average particle size of the pyrolyzable foaming agent is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, further preferably 10 ⁇ m or less, and further preferably 7 ⁇ m or less, It is more preferably 5 ⁇ m or less, still more preferably 4 ⁇ m or less, most preferably 3 ⁇ m or less, and preferably 1 ⁇ m or more. If the volume average particle diameter of the pyrolytic foaming agent is not more than the above upper limit, the foaming ratio of the foamable vinyl chloride resin composition (B) can be improved, the hardness of the resulting skin can be reduced, and the cushioning property can be improved. it can.
  • the volume average particle diameter of the pyrolyzable foaming agent is equal to or greater than the above lower limit, the pyrolyzable foaming agent is excellent in handleability.
  • the “volume average particle diameter” means that the cumulative volume calculated from the small diameter side is 50 in the particle diameter distribution (volume basis) measured using a laser diffraction / scattering particle diameter distribution measuring apparatus. % Particle diameter (median diameter).
  • the content of the pyrolytic foaming agent in the foamable vinyl chloride resin composition (B) is preferably 0.7 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin.
  • the amount is more preferably at least part by mass, further preferably at least 2.1 parts by mass and more preferably at most 4 parts by mass. If the content of the pyrolytic foaming agent is not less than the above lower limit, the foaming ratio of the foamable vinyl chloride resin composition (B) can be improved, the hardness of the resulting skin can be reduced, and the cushioning property can be improved. . On the other hand, if the content of the pyrolytic foaming agent is not more than the above upper limit, the uniformity of the bubbles (cells) is improved. Therefore, the hardness of the resulting skin is reduced almost uniformly regardless of the location, and cushioning properties are improved. Can be increased.
  • the foamable vinyl chloride resin composition (B) preferably contains an acrylic polymer. Since the foamable vinyl chloride resin composition (B) contains an acrylic polymer, the uniformity of bubbles (cells) in the foamed vinyl chloride resin molded sheet (Y) is improved. Regardless of this, it can be reduced substantially uniformly and the cushioning property can be improved.
  • the “acrylic polymer” is a structure derived from a (meth) acrylic acid ester, such as an acrylic acid alkyl ester, a methacrylic acid alkyl ester, an acrylic acid alkoxyalkyl ester, or a methacrylic acid alkoxyalkyl ester.
  • (meth) acrylic acid ester means “acrylic acid ester and / or methacrylic acid ester”.
  • the acrylic polymer is not particularly limited, but it is preferable to use a copolymer (alkyl methacrylate / alkyl acrylate copolymer) of methacrylic acid alkyl ester and acrylic acid alkyl ester.
  • the uniformity of the bubbles (cells) in the foamed vinyl chloride resin molded sheet (Y) is further improved, and thus obtained.
  • the hardness of the skin can be further reduced and the cushioning property can be further improved.
  • the acrylic polymer can be prepared by performing a polymerization reaction using a monomer composition C containing (meth) acrylic acid ester and any other compound as a monomer.
  • (meth) acrylic acid ester monomers that can be used for the preparation of acrylic polymers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, Acrylic acid alkyl esters such as pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate, Methacrylate such as
  • methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate are preferably used.
  • the proportion of the (meth) acrylic acid ester monomer in all monomers in the monomer composition C is preferably 50% by mass or more and 95% by mass or less. If the proportion of the (meth) acrylic acid ester monomer in all the monomers in the monomer composition is equal to or higher than the lower limit, the bubbles (cells) in the foamed vinyl chloride resin molded sheet (Y) are uniform. Since the properties are further improved, the hardness of the resulting skin can be further reduced and the cushioning properties can be further improved. On the other hand, if the proportion of the (meth) acrylic acid ester monomer in all the monomers in the monomer composition is equal to or less than the upper limit, the acrylic polymer is prevented from being fused by heat or the like. be able to.
  • the monomer composition C may contain monomers other than the (meth) acrylic acid ester, and examples thereof include, but are not limited to, ethylenically unsaturated carboxylic acid monomers and ⁇ , ⁇ -unsaturated nitriles. And monomers.
  • the ethylenically unsaturated carboxylic acid monomer at least one of an ethylenically unsaturated carboxylic acid and a salt thereof can be used.
  • the ethylenically unsaturated carboxylic acid include ethylenically unsaturated monocarboxylic acid and derivatives thereof, ethylenically unsaturated dicarboxylic acid and acid anhydrides thereof, and derivatives thereof.
  • the ethylenically unsaturated carboxylate include sodium salts, potassium salts and lithium salts of ethylenically unsaturated carboxylic acids.
  • ethylenically unsaturated carboxylic acid and its salt may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • examples of the ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.
  • examples of the ethylenically unsaturated monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic. Acid, ⁇ -diaminoacrylic acid and the like.
  • Examples of the ethylenically unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
  • Examples of acid anhydrides of ethylenically unsaturated dicarboxylic acids include maleic anhydride, diacrylic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, and the like.
  • examples of the ethylenically unsaturated dicarboxylic acid derivative include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, and fluoromaleic acid.
  • examples of the ⁇ , ⁇ -unsaturated nitrile monomer include acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more.
  • a commercial item can also be used as an acrylic polymer.
  • “methabrene L-1000” manufactured by Mitsubishi Chemical Corporation
  • the content of the acrylic polymer in the foamable vinyl chloride resin composition (B) is preferably 0.01 parts by mass or more and 0.09 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin. More preferably, it is 0.2 mass part or more, More preferably, it is 1 mass part or less, More preferably, it is 0.5 mass part or less. If the content of the acrylic polymer is within the predetermined range, the uniformity of bubbles (cells) in the foamed vinyl chloride resin molded sheet (Y) is further improved, so that the hardness of the resulting skin is further reduced. The cushioning property can be further enhanced.
  • the foamable vinyl chloride resin composition (B) is not particularly limited, and can be prepared by mixing the components described above.
  • the mixing method of the vinyl chloride resin, the foaming agent, and an acrylic polymer, a plasticizer, and other various additives that are further used as necessary is not particularly limited.
  • the method include mixing the components excluding the dusting agent containing the vinyl chloride resin fine particles and the foaming agent by dry blending, and then adding and mixing the dusting agent and the foaming agent.
  • the temperature at the time of dry blending is not specifically limited, 50 degreeC or more is preferable, 70 degreeC or more is more preferable, and 200 degreeC or less is preferable.
  • the temperature at the time of adding a foaming agent can be arbitrarily set within the range with which the desired effect of this invention is acquired according to the kind of foaming agent to be used.
  • the method for producing a skin according to the present invention is a method for producing a skin having a vinyl chloride resin molded sheet (X) and a foamed vinyl chloride resin molded sheet (Y), and a vinyl chloride resin composition comprising a vinyl chloride resin and a plasticizer.
  • a vinyl chloride resin molded sheet (X) is formed using a vinyl chloride resin composition (A) containing a vinyl chloride resin and a predetermined amount of a plasticizer. And usually, the vinyl chloride resin molded sheet (X) is formed by molding the vinyl chloride resin composition (A) into a sheet by a known molding method.
  • the vinyl chloride resin composition (A) the vinyl chloride resin composition (A) used for forming the vinyl chloride resin molded sheet (X) described above in the section of “skin” can be used.
  • powder molding is preferably used, and powder slush molding is more preferably used.
  • the mold temperature at the time of powder slush molding is not particularly limited and is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, and preferably 300 ° C. or lower, and 280 ° C. More preferably, it is as follows.
  • a vinyl chloride resin molded sheet (X) it does not specifically limit, For example, the following methods can be used. That is, the vinyl chloride resin composition (A) is sprinkled on a mold in the above temperature range, left for 5 seconds to 30 seconds, and then the excess vinyl chloride resin composition (A) is shaken off. For 30 seconds to 3 minutes. Thereafter, the obtained vinyl chloride resin molded sheet (X) may be removed from the mold by cooling the mold to 10 ° C. or more and 60 ° C. or less in accordance with the second step described below. However, it does not have to be demolded. The demolded vinyl chloride resin molded sheet is obtained, for example, as a sheet-shaped molded body shaped like a mold.
  • the foamed vinyl chloride resin molded sheet (Y) is formed using the foamable vinyl chloride resin composition (B) on one side in the thickness direction of the vinyl chloride resin molded sheet (X).
  • the foamable vinyl chloride resin composition (B) the foamable vinyl chloride resin composition (B) used for forming the foamed vinyl chloride resin molded sheet (Y) described above in the section of “Skin” is used. be able to.
  • the method for forming the foamed vinyl chloride resin molded sheet (Y) using the foamable vinyl chloride resin composition (B) on one side in the thickness direction of the vinyl chloride resin molded sheet (X) is particularly limited.
  • the foamed vinyl chloride resin composition (B) is molded into a sheet shape by foaming by the known molding method described above in the section of “first step”, and a single foamed vinyl chloride resin molded sheet (Y ), And a method of adhering the foamed vinyl chloride resin molded sheet (Y) to one side in the thickness direction of the vinyl chloride resin molded sheet (X) by a known adhesion method.
  • the following method of continuously performing powder slush molding as the first step and powder slush molding as the second step (sometimes referred to as “double slash molding”). It can also be used.
  • the surplus vinyl chloride resin composition (A) is shaken off from the mold, and further, left at an arbitrary temperature for 30 seconds to 3 minutes.
  • the foamed vinyl chloride resin composition (B) is applied to the mold with the vinyl chloride resin molded sheet (X) attached as a second step without removing the vinyl chloride resin molded sheet (X) from the mold. Sprinkle the powder to foam.
  • the mold temperature when sprinkling the powder of the expandable vinyl chloride resin composition (B) is not particularly limited and is preferably 200 ° C. or higher, more preferably 220 ° C. or higher.
  • the temperature is preferably 300 ° C. or lower, and more preferably 280 ° C. or lower.
  • the surplus foamable vinyl chloride resin composition (B) is shaken off, and further allowed to stand for 30 seconds or more and 3 minutes or less at an arbitrary temperature. Thereafter, the mold is cooled to 10 ° C. or more and 60 ° C. or less, and the obtained skin is removed from the mold.
  • the demolded skin is formed by placing the foamed vinyl chloride resin molded sheet (Y) on one side in the thickness direction of the vinyl chloride resin molded sheet (X).
  • the obtained skin is It is a sheet-like molded body having a two-layer structure that has the shape of a mold as a whole.
  • the foamed polyurethane molded body is used as a backing. A skin that can satisfactorily suppress the heat shrinkage when it is present can be efficiently produced.
  • the skin produced by directly bonding the foamed vinyl chloride resin molded sheet (Y) to the surface on one side in the thickness direction of the vinyl chloride resin molded sheet (X) is produced by the method for producing the skin of the present invention.
  • the method for producing the skin of the present invention is not limited to this.
  • the manufacturing method of the skin of the present invention includes an optional step other than the first step and the second step described above, so that the vinyl chloride resin molded sheet (X) and the foamed vinyl chloride resin molded sheet (Y) can be obtained. It is also possible to produce a skin that is bonded through another resin layer or the like.
  • the laminate of the present invention has a foamed polyurethane molded product and the above-described skin.
  • the laminate of the present invention has a structure in which the above-described foamed vinyl chloride resin molded sheet (Y) is disposed between the foamed polyurethane molded body and the above-described vinyl chloride resin molded sheet (X).
  • the foamed polyurethane molded product is lined on the foamed vinyl chloride resin molded sheet (Y) side of the skin, and the foamed polyurethane molded product and the skin are adjacent in the laminating direction (that is, the foamed polyurethane molded product and The vinyl chloride resin molded sheet (X) is laminated in the laminating direction via the foamed vinyl chloride resin molded sheet (Y)).
  • the laminate of the present invention can suppress thermal shrinkage well. Can do. Therefore, the laminate of the present invention is suitably used as an automobile interior material for automobile interior parts such as an automobile instrument panel and a door trim, and is particularly preferably used for an automobile instrument panel.
  • the lamination method is not particularly limited, and for example, the following method can be used. That is, polymerization is performed by reacting isocyanates and polyols, which are raw materials of the foamed polyurethane molded body, on the surface of the skin on the side where the foamed vinyl chloride resin molded sheet (Y) is disposed, and a known method The polyurethane foam is directly formed on the skin by foaming polyurethane.
  • ⁇ Cell status> The cross section of the foamed vinyl chloride resin molded sheet (Y) was visually observed with an optical microscope, and the cell state was evaluated according to the following criteria.
  • ⁇ Thickness> The thickness was measured by observing the cross sections of the vinyl chloride resin molded sheet (X) and the foamed vinyl chloride resin molded sheet (Y) with an optical microscope.
  • ⁇ Heat resistant shrinkage> Four marks are attached to the laminated body at equal intervals in the longitudinal direction and the short direction of the laminated body, and the distance between the marks is a long caliper (“long type ABS Digimatic Caliper CD manufactured by Mitutoyo Corporation). -60C "). Thereafter, as an accelerated test assuming long-term use, the laminate is stored in a 110 ° C. gear-type oven (“Gear Oven” manufactured by Toyo Seiki Seisakusho), and the heated laminate is removed from the oven after 1000 hours. The distance between the marks provided in the longitudinal direction and the short direction of the laminate was measured with the above long calipers.
  • vinyl chloride resin fine particles as a dusting agent are added, and when the temperature is further lowered to 80 ° C., azodicarboxylic acid as a pyrolytic foaming agent.
  • Amide (volume average particle diameter: 20 ⁇ m) was added to prepare a foamable vinyl chloride resin composition (B).
  • the foamed vinyl chloride resin molded sheet (Y) having a length of 200 mm and a width of 300 mm was removed from the mold. And according to the above-mentioned method, the thickness, specific gravity, and cell state of the obtained foamed vinyl chloride resin molded sheet (Y) were measured or evaluated. The results are shown in Table 1.
  • a vinyl chloride resin was prepared in the same manner as in Production Example 1 except that azodicarbonamide (volume average particle size: 20 ⁇ m) as a pyrolytic foaming agent was not used when preparing the foamable vinyl chloride resin composition (B).
  • a composition and a non-foamed vinyl chloride resin molded sheet were produced. And it evaluated by the method similar to manufacture example 1.
  • FIG. The results are shown in Table 1. Further, from the specific gravity of the non-foamed vinyl chloride resin molded sheet obtained in Comparative Production Example 1 and the specific gravity of the foamed vinyl chloride resin molded sheets (Y) obtained in Production Examples 1 to 12 described above, The expansion ratio of the foamable vinyl chloride resin composition (B) was calculated. The results are shown in Table 1.
  • Example 1 Preparation of vinyl chloride resin composition (A)> Among the blending components for the vinyl chloride resin composition (A) shown in Table 2, components other than the plasticizer and the vinyl chloride resin fine particles as the dusting agent were placed in a Henschel mixer and mixed. Then, when the temperature of the mixture rises to 80 ° C., all of the plasticizer is added, and the temperature is further raised to dry up (the plasticizer is absorbed by the vinyl chloride resin particles, which are vinyl chloride resins, The mixture was further improved.) Thereafter, when the dried-up mixture was cooled to a temperature of 100 ° C. or less, vinyl chloride resin fine particles as a dusting agent were added to prepare a vinyl chloride resin composition (A).
  • the obtained skin was a sheet having a two-layer structure in which the foamed vinyl chloride resin molded sheet (Y) was laminated on one side in the thickness direction of the vinyl chloride resin molded sheet (X). And when the thickness of each of the vinyl chloride resin molded sheet (X) and the foamed vinyl chloride resin molded sheet (Y) constituting the skin was measured, the thickness of the vinyl chloride resin molded sheet (X) was 1.2 mm, foamed The thickness of the vinyl chloride resin molded sheet (Y) was 2.5 mm.
  • the liquid mixture which mixed the obtained polyol mixture and polymethylene polyphenylene polyisocyanate (polymeric MDI) in the ratio from which the isocyanate index becomes 98 was prepared. And the prepared liquid mixture was poured on the skin laid in the metal mold
  • Example 2 In the case of the second step (formation of foamed vinyl chloride resin molded sheet (Y)) in the production of the skin, Example 2 uses the foamable vinyl chloride resin composition (B) obtained in Production Example 5, In Example 3, a skin and a laminate were produced in the same manner as in Example 1 except that the foamable vinyl chloride resin composition (B) obtained in Production Example 9 was used. And it measured by the method similar to Example 1. FIG. The results are shown in Table 1.
  • the laminates of Examples 1 to 3 using the skin formed by arranging the foamed vinyl chloride resin molded sheet on one side in the thickness direction of the vinyl chloride resin molded sheet containing the plasticizer include the plasticizer. It can be seen that heat shrinkage can be well suppressed as compared to the laminate of Comparative Example 1 using a vinyl chloride resin molded sheet alone as the skin.
  • the present invention it is possible to provide a skin that can satisfactorily suppress thermal shrinkage when a foamed polyurethane molded article is used as a backing. Moreover, according to this invention, the laminated body which can suppress the heat contraction of an epidermis favorably can be provided.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

Le but de l'invention est de fournir une peau pouvant avantageusement empêcher un retrait thermique dans des cas où un corps moulé en polyuréthane expansé est utilisé comme support. Cette peau se caractérise en ce qu'elle comprend une feuille moulée en résine de chlorure de vinyle (X) contenant une résine de chlorure de vinyle et un plastifiant, et une feuille moulée en résine de chlorure de vinyle en mousse (Y). La teneur du plastifiant dans la feuille moulée en résine de chlorure de vinyle (X) est d'au moins 50 parties en masse par rapport à 100 parties en masse de la résine de chlorure de vinyle; et la feuille moulée en résine de chlorure de vinyle en mousse (Y) est disposée sur un côté de la feuille moulée en résine de chlorure de vinyle (X) dans le sens de l'épaisseur.
PCT/JP2019/011264 2018-03-28 2019-03-18 Peau, procédé de production de peau et produit en couches WO2019188520A1 (fr)

Priority Applications (5)

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US16/980,846 US20210017373A1 (en) 2018-03-28 2019-03-18 Surface skin, method of producing surface skin, and laminate
CN201980017537.XA CN111886377A (zh) 2018-03-28 2019-03-18 表皮、表皮的制造方法及层叠体
MX2020009641A MX2020009641A (es) 2018-03-28 2019-03-18 Revestimiento superficial, metodo para producir revestimiento superficial y laminado.
EP19774975.7A EP3779033B1 (fr) 2018-03-28 2019-03-18 Peau, procédé de production de peau et produit en couches
JP2020510708A JP7310799B2 (ja) 2018-03-28 2019-03-18 表皮、表皮の製造方法、および積層体

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JP2018062873 2018-03-28
JP2018-062873 2018-03-28

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JP7310799B2 (ja) 2023-07-19
MX2020009641A (es) 2020-10-08
EP3779033A1 (fr) 2021-02-17
US20210017373A1 (en) 2021-01-21
EP3779033B1 (fr) 2023-10-18
CN111886377A (zh) 2020-11-03
EP3779033A4 (fr) 2021-12-22

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